Synthesis and Characterization of Poly(N-propargylsulfamides)

Abstract

A variety of novel N-propargylsulfamide monomers (HC≡CCH2NHSO2R) with alkyl (1−4) or aryl groups (5−10) were polymerized with a Rh catalyst, (nbd)Rh+B-(C6H5)4 (nbd = 2,5-norbornadiene), to provide polymers with moderate molecular weights (3000−15 000) in good yields (above 80%). Polymerization of monomer 4 (R = −(CH2)7CH3) at −15 °C yielded a stereoregular polymer whose cis content was nearly 100%, while the cis content remained 79% at 30 °C. Thus, the stereoregularity of the polymer largely depended on polymerization temperature. On the other hand, polymerization solvents hardly affected stereoregularity. Copolymerization of monomer 4 and N-propargylamide monomer 11 afforded copolymers with various compositions in high yields (above 87%), and the cis contents of the resultant copolymers were located between those of the corresponding homopolymers. The presence of intramolecular hydrogen bonding between the neighboring sulfamide groups was confirmed by IR spectroscopy measured in chloroform, suggesting th...